The interaction of the substituted diene monomers isoprene, C5H8, and myrcene, C10H16, with a lanthanide was probed by examining their chemistry with (C5Me5)2Sm. CH2CHC(Me)CH2reacts with (C5Me5)2Sm to form the bimetallic [(C5Me5)2Sm]2[μ-η2:η4-CH2CHC(Me)CH2], 1. Both (C5Me5)2Sm components in 1 exhibit trivalent metrical parameters. One Sm is oriented toward all four of the dienyl carbon atoms at distances of 2.604(9)−2.799(8) Å, and the other Sm interacts with only two carbons at distances of 2.544(9) and 2.674(9) Å. CH2CHC(CH2)CH2CH2CHCMe2 reacts with (C5Me5)2Sm to form [(C5Me5)2Sm]2[μ-η2:η4-CH2CHC(CH2)CH2CH2CHCMe2], 2, which is similar in structure to 1. The double bond of the pendant olefinic substituent attached to the diene in myrcene does not coordinate. The structures of 1 and 2 are compared to the (C5Me5)2Sm/PhC⋮CPh bimetallic reaction product [(C5Me5)2Sm]2[μ-η1:η1-PhCCPh], 3, which also contains two (C5Me5)2Sm units attached to an unsaturated hydrocarbon, but has equivalent trivalent (C5Me5)2Sm units. Each Sm in 3 interacts with the reduced (PhC⋮CPh)2- primarily through a 2.52−2.54 Å Sm−C bond, although an ortho phenyl carbon is oriented toward each metal at a distance of >2.96 Å.
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